Polymerization and purification of hydrocarbons



July 3l, 1928.

' 1,679,093 s. P. MILLER Er AL POLYMRIZATION kAND PURIFICATION OF HYDRDCARBONS Filed Aug. s, 1926' and nopf a figg/if @g/52,21%, INVENTORS QTTORNEY ily removed by washing,

.of lthe types referred method of polymerizing? with ordinary agitation,

' promptly Yeected if a very tact between the hydrocarbon and the poly-A merizing agent is produced. This can be the polymerization 10 coumarone, indene, etc.,

20 addition to the polymerization, sulfonation We have found 0 sultant resin Patented July 31 ,l 1928.

UNITED ,STATES PATENT oFl-lca i STUART P. MILLER .ANDy JOSEPH BENNETT HILL, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOIRS T0 THE BARRETT COMPANY,

A CORPORATION 0E NEW JERSEY. I

POLYMERIZATION AND PUBIFICATION 0F EIYDBOCABBONS.

replication mea August 5,

Our `invention relates to the polymerization of oils andA relates more particularlysto of solvent naphthas and benzol, toluol, xylol and to the purifying of 5 other similar hydrocarbons bythe polymerization, or' similar conversion, into easily separable compounds, of the 4impurities in said hydrocarbons. By the use of our processV the polymerizable constituents, such as in ynaphtha or the polymerizable impurities in benzol, toluol, xylol, etc., may be substantially continuously polymerized or converted into other compounds in ,a very rapid and eiiicient manner.

5 This application is in part a continuation of our application #676,509, filed November as, 1923. Y A

, Those skilled in the artwill recognize that in the purification of these hydrocarbons, in

of certain-of the impurities will occur; certain unsaturated compounds are also converted into tarry bodies. All of these conversion products may, subsequently` be easdistillation and other well known means. en, therefore, reference is hereinafter made to polymerization/it is intended to include, besides actual polymerization, such other reactions to as ordinarily occur in the purification `of the class of hydrocarbons above mentioned. t

In our Patent No. 1,464,851 we have shown the advantage of the continuous 'iby continuously naphtha and a polyas sulp'huric acid, a suitable agitator Aor other vessel.

that the quality of the reis materially improved if the rate of this flow through the polymerizing apparatus is increased. Thi lflow is limited, however,.by the speed with which polymerizationcan be accomplish running an oil, such as merizlng agent, `such through ed. This reaction even though very vigorous, takes an appreciable time, say onehalf minute, to 'go to completion.

VWe have found that' advantageous results are pobtained. and polymerization is more intimate con- '..shape of a trvuncated 1926. Serial N0. 127,226.

done by causingia mixture of the hydrocarbon and sulfuric acid or other polymerizing agent, such as anhydrous aluminum chloride, to pass between surfaces that have a narrow or very restricted space therebetween, one of these surfaces moving rapidly past the other, or the mixture may be emulsitied in any other suitable way which willrcause thorough and lintimate contact ofv the particles with each other, as for instance by the use of the equipment commonly used for manufacture of emulsions and suspensions. v y y the invention more In order to explain clearly, devicesy will be mentioned which 'may be utilized for bringing'about the intimate mixing or contacting, in a continuous manner, of the particles of hydrocarbon and polymerlzmg agent, although itis to be understood that the emulsification may be effected in other ways than those illustrated. In the drawings,

Fig. 1 is a vertical section through a device that may be used for carrying out the process;

\ Fig. 2 is a vertical section through a different form of device; and

Fig. 3 is a section along the line aV--a of Fig. 2.

We shall describe the operation of the' deviceshereina-fter mentioned, in connection with t e polymerization vof, naphtha although uch devices are equally applicable to, and would be operated similarly in ,the polymerization or washing of other hydrocarbons such as benzol, toluol, xylol, etc.'

In the drawings reference Vcharacter 1 designates a stationary casing or stator that is provided with an let tube 3. The casing 1 .is closed'1 at both two relatively moving inlet tube 2 and an outends and its intermediate portion is of the I cone, the inside sulface 4 of which is smooth.. The casing 1 is provided with holes 5 and 6 having stuifing boxes 7 and 8 therein through which a shaft 9 is adapted to pass. AThe shaft 9 is mounted in bearings 10 and 11 and may be driven by a motor or p ey -12 or in any other convenient manner face comin close proximity 'Ato the inner and carries a rotor 13 of such a'shape that its peripheral. sur- 'are also preferably very-rapidly and th is withdrawn .through the pipe 17. v y of course, that one. f A. v suitably removable sov that the parts to be-` .and polymerlzmg agentthroug'h the emulsi- Y 4fier illustrated A mixture. partakes of` ameandering path be- `In their rotation,

placed in ing. merel a-stator@ -V As' a particular .illustration of the .sort of.

passage, (exaggerated as to size in the drawings) between' the two. This passage is preferably only a few thousandths of an inch wide, for instance five thousandths to fifteen thousandths oflan more with fairly Asatisfactory results. The mixture of naphtha and polymerizingagent is introduced through `the inlet 2 and the rotor 13 is driven at a relatively high velocity which may be about 3000 to 15000 feet per minute, more or less, at its periphery. The mixture is thereby either thoroughly emulsified or the particles of one mixed in an extremely finely subdivided condition in the other one so that the particles of the two respective materials are .brought into intimate contact thusr causing the polymerization to take place rapidly. The polymerized product is then lwithdrawn through the pipe 3.

Reference character 15, Figs. 2 and 3, represents a stationary casing or stator that is provided with an inlet pipe 16 vand an outlet pipe 17. It has openings 18 and 19 in which there are stuffing boxes 20 and 20 through which the shaft 22 is adapted to pass. The shaft 22-is mounted in bearings 23and 24.- and may be driven by a motor o r pulley 25 or in any other convenient manner. The shaft 22 also carries a'series of spokes 26 preferably square in cross section. These spokes alternate with pin or projections 27 attached to the inside of the`casing 21, which square in cross section. he spokes 26V, pass very close to the pins or projections 27 leaving spaces therebetween of only a few thousandths of an inch (exaggerated as to size in the drawings). The mixture of naphtha and polymerizing agent is introduced through the inlet pipe 16 and while the shaft 22 is being driven at vhigh velocity the particles of the mixture are intimately contacted so that' the polymerization takes place product eA polymerized Itis to be understood or both ends of the stators 1 and 15 are made located in [the respective stators may be position therein, the drawings bey a Adiagranilnatic showing ofl carryingout vour process.

processr may! also Abe carried ou`t, for y. passing-,al'mixture of naphthaq means for The.' example, y

1n application t Serial N o. 678,100, iiledDecember 3, l19,23 in .which the cause of ringsl on a' rotor revolving between corresponding concentric xrings mounted on.

ofthe components are..

`such materialsl asY sulfuric acid of varym minute .subdivision v intended to be that stem-apparatus or condinaphtha vthat can be readily treated in this way, it may be mentioned that solvent naphtha containing. from about 25%. of polymerizable constituents such ascoumarone, indene, etc., may, with about 3% by weight of 660 B.` sulfuric acid, be introduced into and passed thru a. device of the type described for about l0 seconds Whereupon. polymerization will be effected. The polymerized product may then be permitted to settle and the'spent acid drawn ofi` after which the product may be neutralized and distilled in the ordinary and Well known ways.V

It has been found that resin produced in this Way has a. better color or is lighter in color than resins produced by processes in which a' longer time is required for thepolymerization to take place, and that the melting point ofthe resin produced by this process is increased above that which would beobpIOCeSSeS.

When it is desired treat such hydro- Y l carbons as benzol, toluol or xylol with a reagent such as sulphuric acid which willconv ert the impurities in the hydrocarbons into easilyseparable compounds, bons may be treated in a manner very much similar to the Way in-which we would polymerize A.the polymerizable constituents in solvent naphtha.

For instance benzol to'ether with about 8 to 10% of66o Be.- vsulp iuric acid may be introduced into the type of device above described. The mixture is permitted to pass thru the device at such a speed that each particle of. the .mixture vice for about 10 seconds, the relatively moving. surfaces being maintained at'J the speeds mentioned. The impurities in the benzol are thusI polymerized kor` converted and may easily separated fromthe mixture by meth- -ods well known .to those skilled in the art,

such as by washing followed by distillation. Toluol, xylol and similar hydrocarbons may Abe treated in a similar manner, amount of sulfuric acid in the Ordinar way. In the claims appended hereto, lya iiydrocarbon includes the above mentioned hydrocarbons and reasonable equivalents there- `of and impurities includes-the coumarone, indene, etc., in naphtha as well as the recogn ized .impuritiessuchl vas theunsaturated and easily sulfonatable materials ordinarily removed from' the hydrocarbonY by the usual. purification methods. Polymer.izing agent or reagentv is'intended to include strengths, anhydrous aluminum-chloride an other -materials recognized.y by those` skilled in the art as valuable for purification ofhydrocarbons. Emulsifying, emulsifer or of 4one infthe'oth'er is remains in thedevarying the Athe hydrocarother.

5. T he process which comprises agitating sulfurlc acid and naphtha containing polymerlzable constituents sufficiently to form a minute subdivision of one in the other.

6. The process which comprises treating a mixture of a polymerizing agent and naphtha containing polymerizable constituvents by passing the same between surfaces spaced apart from 0.005 to 0.10 of-,an inch and moving relative to each other at a velocity sufficient to emulsify said polymerizing agent and naphtha.

7. The process which comp-rises treatinga mixture of sulfuric acid and naphtha containing polymerizable constituents by passing the same between surfaces spaced apart from 0.005 to 0.10 of an inch and moving relative to each other at a velocity sufficient to emulsiy said acid and naphtha.

. 8. The process which comprises treating a mixture of a polymerizing agent and naphtha containing polymerizable constituents by passingthe same between surfaces moving relative to each other at a 'velocity above 50 feet per second, said surfaces being so spaced as to cause' emulsication oi said polymerizin 4 agent and naphtha when lpassed there tween.' f

9.The process which comprises treatin a mixture of a. polymerizing agent an napht-ha containing Lpolymerizable constituentsfbypassing the same between surfaces moving relative to each other vat a velocity above 50 feet per-second .and spaced apart from 0.005 to 0.10 of an inch.-

'10. The process which comprises mixing about 3% by weight of approximately 66 B. sulfuric acid withnaphtha containing polymerizable' constituents and :[inely dividing one in the other.

11. The process which comprises mixing about 3% by weight of approximately 66 B. sulfuric acid with naphtha containing polymerizable constituents and emulsifying,

neutralizing and distilling the same. p

12. The process of lpolymerizing naphthawhich comprises passing naphthal and a polymerizing agent substantially j continuously through an emulsifier.

13. The process of -polymerizing naphtha which comprises passing naphtha and sulfuric acid substantially continuously through an emulsiier. l

14; The )process whichcomprises treating a mixture of a polymerizing agent and naphtha containing polymerizable constituents by passing the same between surfaces spaced apart from 0.005 to 0.015 of an inch and moving relative to each other at a.

velocity suiicient to emulsify said polymery =izing agent and naphtha.

15. The process of l=polymerizing oils which comprises passingthe yoil and a polymerizing agent substantially continuously` thru an emulsiier;

16. The process which comprises emulsifying a hydrocarbon containing impurities 'and a liquid rea-gent that will react upon the impurities without appreciable reaction upon said hydrocarbon. v

17. The process. which comprises intro-- ducing into a` receptacle, a. hydrocarbon containing impurities and -a liquid-reagent that will react'upon theimpurities without appreciable reaction upon said hydrocarbon "and mixing said materials suiciently to form a minute -sub-dlvislonof one 1n the- Other.' A l In testimony whereof wel aixV our s1gnatures.

y STUART P. MILLER.

JOSEPH BENNETT HILL. 

